Unsaturated amorphous polyesters based on certain dicidol isomers

ABSTRACT

The invention relates to unsaturated, amorphous polyesters based on certain dicidol isomers and on saturated and/or unsaturated dicarboxylic acids.

The invention relates to unsaturated, amorphous polyesters based oncertain dicidol isomers and acids.

Unsaturated polyester resins (UP resins) are well known. They areprepared by condensing saturated and unsaturated dicarboxylic acids ortheir anhydrides with diols. Their properties depend substantially onthe type and ratio of the starting materials.

The bearers of the polymerizable double bonds used are usuallyα,β-unsaturated acids, primarily maleic acid and its anhydride orfumaric acid; unsaturated diols are of minor importance. The higher thecontent of double bonds, i.e. the smaller the separation of the doublebonds in the chain molecules, the more reactive the polyester resin. Itpolymerizes very rapidly with intense development of heat and extensivecontraction to give a highly crosslinked and therefore comparativelybrittle end product. For this reason, the reactive double bonds in thepolyester molecule are “diluted” by co-condensing saturated aliphatic oraromatic dicarboxylic acids. The alcohol components used arestraight-chain and branched diols. The individual UP resin types differnot only in the components used to prepare them but also in the ratio ofsaturated to unsaturated acids which determines the crosslinking densityin the polymerization, the degree of condensation, i.e. the molar mass,the acid number and the OH number, i.e. the type of end groups in thechain molecules, the monomer content and the type of additives(Ullmann's Encyclopedia of Industrial Chemistry, VOL A21, p. 217ff.,1992).

UP resins based on dicidol as the diol component are known, for example,from DE 924 889, DE 953 117, DE 22 45 110, DE 27 21 989, EP 114 208, EP934 988.

It is an object of the present invention to provide novel unsaturatedand amorphous polyester resins from the multiplicity of possibilitiesand diversity of the prior art which are also readily soluble withoutcloudiness in many solvents and are transparent as solids. This objectis achieved as will be illustrated henceforth.

The invention provides unsaturated, amorphous polyesters substantiallycomprising at least one α,β-unsaturated dicarboxylic acid component andone alcohol component,

wherein

-   the alcohol component comprises a dicidol mixture of the isomeric    compounds 3,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane,    4,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane and    5,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane,-   where each isomer may be present in the mixture in a proportion of    from 20 to 40% and the sum of the three isomers is from 90 to 100%,-   and at least 5% of the mixture is present in the alcohol component    of the polyester.

The invention also provides a process for preparing unsaturated,amorphous polyesters substantially comprising at least oneα,β-unsaturated dicarboxylic acid component and one alcohol component,

wherein

-   the alcohol component comprises a dicidol mixture of the isomeric    compounds 3,8-bis(hydroxymethyl)tricyclo-[5.2.1.0^(2,6)]decane,    4,8-bis(hydroxymethyl)tricyclo-[5.2.1.0^(2,6)]decane and    5,8-bis(hydroxymethyl)tricyclo-[5.2.1.0^(2,6)]decane,-   each isomer may be present in the mixture in a proportion of from 20    to 40% and the sum of the three isomers is from 90 to 100%,-   and at least 5% of the mixture is present in the alcohol component    of the polyester,-   by reacting the starting components at a temperature of from 150 to    270° C., preferably in an inert gas atmosphere, where the inert gas    has an oxygen content of less than 50 ppm.

The unsaturated, amorphous polyester resins according to the inventionare obtained by reacting the alcohol component with the acid component.

According to the invention, the alcohol component used is a dicidolmixture of the isomeric compounds3,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane,4,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane and5,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane, where each isomermay be present in the mixture in a proportion of from 20 to 40% and thesum of the three isomers is from 90 to 100%, preferably from 95 to 100%,and at least 5% of the mixture is present in the alcohol component ofthe polyester. The isomer content of the dicidol mixture may bedetermined qualitatively and quantitatively, for example by GC analysis,or quantitatively by separating by means of preparative GC or HPLC andsubsequent NMR spectroscopy. All corresponding isomers of dicidol in the9-position are equally suitable but, owing to the mirror symmetry of theabove mentioned isomers, like the cis- and trans-isomers, cannot bedifferentiated under normal, practical conditions.

The dicidol mixture may further comprise up to 10% of further isomers ofdicidol and/or trimeric and/or higher isomeric diols of the Diels-Alderreaction product of cyclopentadiene. The alcohol component preferablyconsists of 20%, of 50%, preferably of 90%, more preferably of 100%, ofdicidol mixture which more preferably comprises from 95 to 100% of theabovementioned three isomeric compounds.

In addition to the dicidol mixture, the alcohol component may comprisefurther linear and/or branched, aliphatic and/or cycloaliphatic and/oraromatic diols and/or polyols. The additional alcohols used arepreferably ethylene glycol, 1,2- and/or 1,3-propanediol, diethyleneglycol, dipropylene glycol, triethylene glycol or tetraethylene glycol,1,2- and/or 1,4-butanediol, 1,3-butylethylpropanediol,1,3-methylpropanediol, 1,5-pentanediol, cyclohexanedimethanol, glycerol,hexanediol, neopentyl glycol, trimethylolethane, trimethylolpropaneand/or pentaerythritol.

The starting acid component present in the unsaturated, amorphouspolyester resins according to the invention comprises at least oneα,β-unsaturated dicarboxylic acid. The unsaturated polyester resinspreferably comprise citraconic acid, fumaric acid, itaconic acid, maleicacid and/or mesaconic acid.

In addition, aromatic and/or aliphatic and/or cycloaliphaticmonocarboxylic acids and/or dicarboxylic acids and/or polycarboxylicacids may also be present, for example phthalic acid, isophthalic acid,terephthalic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid,sebacic acid, methyltetrahydrophthalic acid, methylhexahydrophthalicacid, hexahydrophthalic acid, tetrahydrophthalic acid,decanedicarboxylic acid, adipic acid, azelaic acid, isononanoic acid,2-ethylhexanoic acid, pyromellitic acid and/or trimellitic acid.Preference is given to phthalic acid, hexahydrophthalic acid,tetrahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acidand/or azelaic acid.

The acid component may partly or entirely consist of anhydrides and/oralkyl esters, preferably methyl esters.

In general, the alcohol component is present in a molar ratio of from0.5:1 to 2.0:1 to the acid component, preferably from 0.8:1 to 1.5:1.The reaction of the alcohol component more preferably takes place in amolar ratio of from 1.0:1 to 1.1:1 to the acid component.

The unsaturated, amorphous polyesters according to the invention mayhave an acid number of from 1 to 200 mg KOH/g, preferably from 1 to 100mg KOH/g, more preferably from 1 to 50 mg KOH/g, and an OH number offrom 1 to 200 mg KOH/g, preferably from 1 to 100 mg KOH/g, morepreferably from 1 to 50 mg KOH/g.

The Tg of the unsaturated, amorphous polyesters according to theinvention varies from −30 to +80° C., preferably from −20 to +50° C.,more preferably from −10 to +40° C.

In one preferred embodiment I, the unsaturated polyesters (UP resins)according to the invention consist of an alcohol component comprising atleast 90%, preferably 95%, more preferably 100%, of the dicidol mixtureof the isomeric compounds3,8-bis-(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane,4,8-bis-(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane and5,8-bis-(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane, and of fumaricacid and/or maleic acid/anhydride. In a further preferred embodiment II,the polyesters comprise the abovementioned starting components as underI, but additionally a further acid selected from adipic acid andphthalic acid/anhydride, where the ratio of α,β-unsaturated acid to theadditional acid may vary from 2:1 to 1:4. Preference is given to ratiosof approx. 1:1 to 1:2. These polyesters generally have acid numbers offrom 1 to 200 mg KOH/g, preferably 1-100 mg KOH/g, more preferably 1-50mg KOH/g, OH numbers of from 1 to 200 mg KOH/g, preferably 1-100 mgKOH/g, more preferably 1-50 mg KOH/g, and a Tg of from −30 to +80° C.,preferably from −20 to +50° C., more preferably from −10 to +40° C.

The polyesters according to the invention may also comprise assistantsand additives which are selected from inhibitors, water and/or organicsolvents, neutralizing agents, surface-active substances, oxygenscavengers and/or radical scavengers, catalysts, light stabilizers,color brighteners, photosensitizers, thixotropic agents, antiskinningagents, defoamers, antistats, thickening agents, thermoplasticadditives, dyes, pigments, flame retardants, internal release agents,fillers and/or blowing agents.

The polyesters according to the invention are prepared by(semi)continuous or batchwise esterification of the starting acids andalcohols in a one-stage or two-stage procedure.

The process according to the invention, as described above, ispreferably operated in an inert gas atmosphere at from 150 to 270° C.,preferably from 160 to 230° C., more preferably from 160 to 200° C. Theinert gas used may be nitrogen or a noble gas, in particular nitrogen.The inert gas has an oxygen content of less than 50 ppm, in particularless than 20 ppm.

The polyester resins according to the invention are further illustratedby the examples which follow:

EXAMPLES

Starting component: dicidol mixture (claim 1) in an isomeric ratio ofapproximately 1:1:1

Example 1

Decanedicarboxylic acid and fumaric acid (ratio 0.6:0.4) are reactedwith dicidol in a ratio of 1:1.05 at 180° C. in a nitrogen atmosphereuntil an acid number of 24 mg KOH/g and an OH number of 34 mg KOH/g areattained. To this end, the fumaric acid is initially esterified withdicidol over the course of one hour and then the dodecanedicarboxylicacid is added. M_(n)=2200 g/mol, M_(w)=5500 g/mol, glass transitiontemperature 4° C.

Example 2

Adipic acid and maleic acid (ratio 1:1) are reacted with dicidol in aratio of 1:1.05 at 180° C. in a nitrogen atmosphere until an acid numberof 26 mg KOH/g and an OH number of 37 mg KOH/g are attained. To thisend, the maleic acid is initially esterified with dicidol over thecourse of one hour and then the adipic acid is added. M_(n)=1800 g/mol,M_(w)=4300 g/mol, glass transition temperature 12° C.

1. An unsaturated, amorphous polyester comprising at least oneα,β-unsaturated dicarboxylic acid component and one alcohol component,wherein the alcohol component comprises a dicidol mixture of theisomeric compounds 3,8-bis(hydroxymethyl)-tricyclo[5.2.1.0^(2,6)]decane,4,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane and5,8-bis-(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane, where each isomermay be present in the mixture in a proportion of from 20 to 40% and thesum of the three isomers is from 90 to 100%, and at least 5% of themixture is present in the alcohol component of the polyester.
 2. Theunsaturated, amorphous polyester as claimed in claim 1, wherein up to10% of further isomers of dicidol and/or trimeric and/or higher isomericdiols of the Diels-Alder reaction product of cyclopentadiene arepresent.
 3. The unsaturated, amorphous polyester as claimed in claim 1,wherein the acid component additionally comprises aromatic and/oraliphatic and/or cycloaliphatic monocarboxylic acids and/or dicarboxylicacids and/or polycarboxylic acids.
 4. The unsaturated, amorphouspolyester as claimed in claim 1, wherein the acid component consistspartly or entirely of anhydrides and/or alkyl esters.
 5. Theunsaturated, amorphous polyester as claimed in claim 1, wherein thealcohol component comprises further linear and/or branched, aliphaticand/or cycloaliphatic and/or aromatic diols and/or polyols.
 6. Theunsaturated, amorphous polyester as claimed in claim 1, wherein theα,β-unsaturated dicarboxylic acid present is citraconic, fumaric,itaconic, maleic and/or mesaconic acid.
 7. The unsaturated, amorphouspolyester as claimed in claim 1, wherein the additional acids presentare phthalic acid, isophthalic acid, terephthalic acid,1,4-cyclohexanedicarboxylic acid, succinic acid, sebacic acid,methyltetrahydrophthalic acid, methylhexahydrophthalic acid,hexahydrophthalic acid, tetrahydrophthalic acid, dodecanedicarboxylicacid, adipic acid, azelaic acid, isononanoic acid, 2-ethylhexanoic acid,pyromellitic acid and/or trimellitic acid, their anhydrides and/ormethyl esters.
 8. The unsaturated, amorphous polyester as claimed inclaim 1, wherein the additional alcohols present are ethylene glycol,1,2- and/or 1,3-propanediol, diethylene, dipropylene, triethylene glycolor tetraethylene glycol, 1,2- and/or 1,4-butanediol,1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol,cyclohexanedimethanol, glycerol, hexanediol, neopentyl glycol,trimethylolethane, trimethylolpropane and/or pentaerythritol.
 9. Theunsaturated, amorphous polyester as claimed in claim 1, wherein at least20% of the alcohol component consists of the isomeric compounds.
 10. Theunsaturated, amorphous polyester as claimed in claim 1, wherein at least50% of the alcohol component consists of the isomeric compounds.
 11. Theunsaturated, amorphous polyester as claimed in claim 1, wherein at least90% of the alcohol component consists of the isomeric compounds.
 12. Theunsaturated, amorphous polyester as claimed in claim 1, wherein at least100% of the alcohol component consists of the isomeric compounds. 13.The unsaturated, amorphous polyester as claimed in claim 1, wherein theα,β-unsaturated acid component present is fumaric acid and/or maleicacid/anhydride.
 14. The unsaturated, amorphous polyester as claimed inclaim 1, wherein the further dicarboxylic acid component present isadipic acid and/or phthalic acid/anhydride.
 15. The unsaturated,amorphous polyester as claimed in claim 1, wherein the alcohol componentis present in a molar ratio of from 0.5:1 to 2.0:1 to the acidcomponent.
 16. The unsaturated, amorphous polyester as claimed in claim1, wherein the alcohol component is present in a molar ratio of from0.8:1 to 1.5:1 to the acid component.
 17. The unsaturated, amorphouspolyester as claimed in claim 1, wherein the alcohol component ispresent in a molar ratio of from 1.0:1 to 1.1:1 to the acid component.18. The unsaturated, amorphous polyester as claimed in claim 1, whichhas an acid number of from 1 to 200 mg KOH/g.
 19. The unsaturated,amorphous polyester as claimed in claim 1, which has an OH number offrom 1 to 200 mg KOH/g.
 20. The unsaturated, amorphous polyester asclaimed in claim 1, wherein assistants and additives are present. 21.The unsaturated, amorphous polyester as claimed in claim 1, whereinassistants and additives are present which are selected from inhibitors,water and/or organic solvents, neutralizing agents, surface-activesubstances, oxygen scavengers and/or radical scavengers, catalysts,light stabilizers, color brighteners, photosensitizers, thixotropicagents, antiskinning agents, defoamers, antistats, thickening agents,thermoplastic additives, dyes, pigments, flame retardants, internalrelease agents, fillers and/or blowing agents.
 22. The unsaturated,amorphous polyester as claimed in claim 1, wherein the alcohol componentconsists of at least 90% of the dicidol mixture, and fumaric acid and/ormaleic acid(anhydride) are present in a diol/acid ratio of from 0.9:1 to1.1:1.
 23. The unsaturated, amorphous polyester as claimed in claim 22,wherein adipic acid and/or phthalic acid/anhydride are additionallypresent as the acid component in a ratio of α,β-unsaturated toadditional acid of from 3:1 to 1:4.
 24. A process for preparingunsaturated, amorphous polyesters substantially comprising at least oneα,β-unsaturated dicarboxylic acid component and one alcohol component,wherein the alcohol component comprises a dicidol mixture of theisomeric compounds 3,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane,4,8-bis(hydroxymethyl)tricyclo[5.2.1.0^(2,6)]decane and5,8-bis(hydroxymethyl)tricyclo [5.2.1.0^(2,6)]decane, each isomer may bepresent in the mixture in a proportion of from 20 to 40% and the sum ofthe three isomers is from 90 to 100%, and at least 5% of the mixture ispresent in the alcohol component of the polyester, by reacting startingcomponents at a temperature of from 150 to 270° C.
 25. The process asclaimed in claim 24, wherein the reaction is effected in an inert gasatmosphere.
 26. The process as claimed in claim 24, wherein the inertgas has an oxygen content of less than 50 ppm.
 27. (canceled)